WO2021136228A1

WO2021136228A1 - Method for preparing copper ferrite/zeolite spinel composite material and use thereof

Info

Publication number: WO2021136228A1
Application number: PCT/CN2020/140597
Authority: WO
Inventors: 马军; 国谦; 邱微; 李冬; 何海洋; 郭忠凯; 张家明; 刘坪鑫
Original assignee: 哈尔滨工业大学; 哈尔滨工业大学水资源国家工程研究中心有限公司
Priority date: 2019-12-31
Filing date: 2020-12-29
Publication date: 2021-07-08
Also published as: CN111068739B; CN111068739A

Abstract

Disclosed are a method for preparing a copper ferrite/zeolite spinel composite material and the use thereof, which relates to the technical field of water treatment. The present invention provides a method for preparing a copper ferrite/zeolite spinel composite material, and the use thereof, and thus, a practical, convenient and efficient catalyst is prepared, which catalyst can effectively catalyze ozone oxidation so as to degrade an organic contaminant, atrazine, in water. The method comprises: adding copper nitrate and iron nitrate to anhydrous ethanol, stirring same, then adding anhydrous citric acid, and then stirring same to obtain a copper ferrite mixed solution in a sol state; and adding a natural zeolite powder into the copper ferrite mixed solution in a sol state, continuing stirring until the copper ferrite mixed solution in a sol state is evaporated to dryness, then grinding same, then calcining same at a high temperature, and finally, air cooling same to room temperature and grinding same to obtain the copper ferrite/zeolite spinel composite material. By means of the present invention, a method for preparing a copper ferrite/zeolite spinel composite material and the use thereof can be obtained.

Description

Preparation method and application of copper ferrite/zeolite spinel composite material

Technical field

The invention relates to the technical field of water treatment, in particular to a preparation method and application of a copper ferrite/zeolite spinel composite material.

Background technique

The traditional advanced oxidation technology uses ·OH as the main active substance to degrade pollutants. ·OH has a strong oxidizing property and non-selectivity, which makes it react quickly with organic matter, and the oxidation rate constant is mostly 108M ^-1 s ^-1 ～1010M ^-1 s ^-1 . The heterogeneous catalytic ozonation process, as one of the advanced oxidation technologies, is also based on promoting the decomposition of ozone to ·OH to improve the removal of organic matter. The heterogeneous catalytic ozonation process does not require the addition of complex chemical agents to the reaction system, and the solid catalyst added to the reaction device is easy to recycle and process. At the same time, it has the characteristics of simple operation and convenient maintenance, so it has the advantages in the actual water treatment process. Good application prospects.

Atrazine (ATZ), also known as atrazine, is a triazine pesticide herbicide. It is widely used in the control and prevention of weeds in corn, orchards and farmland. Due to its excellent herbicidal efficacy, low price and easy It has become one of the most widely used and most important herbicides in the world. my country is a large agricultural country. The production and use of pesticides are among the top in the world, accounting for about one-tenth of the world's total output. Atrazine has been used in my country since the early 1980s, and the scope of use has continued to expand in recent years. Studies have shown that 20% to 70% of the pesticides applied will remain in the soil for a long time, and atrazine has soil leaching properties, which can easily penetrate into the aquifer through rainfall or surface water leaching to produce bioaccumulation. Cause water pollution. If the human body is exposed to atrazine for a long time, the immune system, lymphatic system, reproductive system and endocrine system will be affected, which may cause malformations and induce organism mutations, which will seriously endanger human health. Therefore, it is important to develop effective treatment technologies to remove atrazine from the water.

There are three main methods for the degradation and removal of atrazine: physical adsorption, chemical oxidation and biodegradation, but the above methods have the problems of high cost, slow experimental process and incomplete degradation of atrazine. Using the adsorption method, it is difficult to prepare cost-effective adsorbents, and there are also analytical problems; the oxidation method is used, and the operation and treatment costs of the process are high, which limits their promotion to a certain extent; whether the use of microbial degradation will produce Concerns about secondary pollution and whether microorganisms will release substances harmful to humans.

Summary of the invention

The invention provides a preparation method and application of a copper ferrite/zeolite spinel composite material, and prepares a practical, convenient and efficient catalyst, which can effectively catalyze the ozone oxidation and degradation of organic pollutant atrazine in water.

The preparation method of copper ferrite/zeolite spinel composite material is completed according to the following steps:

1. Under the temperature condition of 90℃～100℃, add copper nitrate and ferric nitrate to absolute ethanol, stir evenly, then add anhydrous citric acid, and stir evenly to obtain copper ferrite sol state mixture, so The molar ratio of copper nitrate to ferric nitrate is 1:2, the ratio of the total amount of copper nitrate and ferric nitrate to the volume of absolute ethanol is 11.49mmol: (100mL～120mL), the volume of absolute ethanol is relative to that of anhydrous ethanol. The ratio of the amount of citric acid is (100mL～120mL): 7.66mmol;

2. Under the temperature condition of 90℃～100℃, add natural zeolite powder to the copper ferrite sol mixture at a rate of 10mg/s～20mg/s, and continue to stir until the copper ferrite sol mixture is evaporated to dryness. Then it was ground, heated to 400°C, and calcined at 400°C for 8 hours, and finally cooled to room temperature in air, and ground to obtain a copper ferrite/zeolite spinel composite material. The copper ferrite sol-state mixture contained iron The mass ratio of acid copper to natural zeolite powder is 1:(1～5).

The beneficial effects of the present invention:

1. In the present invention, the copper ferrite/zeolite spinel composite material is prepared by the impregnation-sol-gel method. Compared with a single ozone system, a single natural zeolite catalytic ozone system and a single copper ferrite catalytic ozone system, the copper ferrite/ The zeolite spinel composite material greatly improves the efficiency of ozone degradation of atrazine, and the degradation rate of atrazine is increased by about 30% within 40 minutes. When the mass ratio of copper ferrite to natural zeolite powder is 1:1, it is prepared The copper ferrite/zeolite spinel composite material catalyzes the degradation of atrazine in water by ozonation, and completes the degradation in 120 minutes; and the copper ferrite/zeolite spinel composite material prepared by the present invention has stable performance and has stable performance after the reaction. Only 0.05mg/L～0.09mg/L metal ions dissolve in the aqueous solution.

2. The invention prepares the copper ferrite/zeolite spinel composite material, the preparation method is simple, the raw material price is low, it has strong magnetism, is easy to recycle, and can be reused.

The invention can obtain the preparation method and application of the copper ferrite/zeolite spinel composite material.

Description of the drawings

Figure 1 is a comparison diagram of the removal efficiency of atrazine in the 1#～6# reactor in the comparative experiment, C ₀ is the initial concentration _{of atrazine, and C t} is the concentration of atrazine at any time t; ■ represents a single ozone system, ● represents a single natural zeolite catalytic ozone system, ▲ represents a single copper ferrite catalyzed ozone system, ▼ represents a copper ferrite/zeolite spinel composite catalyzed ozone system prepared in Example 3, ◆ represents an example Two prepared copper ferrite/zeolite spinel composite material catalytic ozone system,

Representing the catalytic ozone system of the copper ferrite/zeolite spinel composite prepared in Example 1;

Figure 2 is the copper ferrite/zeolite spinel composite material prepared in Example 1, the removal efficiency of atrazine in water within 0-120min, C ₀ is the initial concentration of atrazine, and C _t is A The concentration of Trazine at any time t, ■ represents the catalytic ozone system of the copper ferrite/zeolite spinel composite material prepared in Example 1.

Detailed ways

Specific embodiment 1: The preparation method of the copper ferrite/zeolite spinel composite material of this embodiment is completed in the following steps:

1. Under the temperature condition of 90℃～100℃, add copper nitrate and ferric nitrate to absolute ethanol, stir evenly, then add anhydrous citric acid, and stir evenly to obtain copper ferrite sol state mixture, so The molar ratio of copper nitrate to ferric nitrate is 1:2, the ratio of the total amount of copper nitrate and ferric nitrate to the volume of anhydrous ethanol is 11.49mmol: (100mL～120mL), the volume of anhydrous ethanol is relative to that of anhydrous ethanol. The ratio of the amount of citric acid is (100mL～120mL): 7.66mmol;

The beneficial effects of this embodiment:

1. In this embodiment, the copper ferrite/zeolite spinel composite material is prepared by the impregnation-sol-gel method. Compared with a single ozone system, a single natural zeolite catalyzed ozone system, and a single copper ferrite catalyzed ozone system, the copper ferrite /Zolite spinel composite material greatly improves the efficiency of ozone degradation of atrazine, and the degradation rate of atrazine is increased by about 30% within 40 minutes. When the mass ratio of copper ferrite to natural zeolite powder is 1:1, prepare The obtained copper ferrite/zeolite spinel composite material catalyzes the degradation of atrazine in water by ozonation, and completes the degradation in 120 minutes; and the copper ferrite/zeolite spinel composite material prepared in this embodiment has stable performance and is in the reaction Only 0.05mg/L～0.09mg/L of metal ions dissolve in the aqueous solution.

2. In this embodiment, the copper ferrite/zeolite spinel composite material is prepared with simple preparation method, low raw material price, strong magnetism, easy recycling, and reusable use.

Specific embodiment two: this embodiment is different from specific embodiment one in that: in step one, under the temperature condition of 90℃～100℃, copper nitrate and ferric nitrate are added to the absolute ethanol at 120r/min Stirring evenly at a stirring rate of ~180r/min.

The other steps are the same as in the first embodiment.

Specific embodiment three: this embodiment is different from specific embodiment one or two in that: adding anhydrous citric acid as described in step one, and then stirring uniformly at a stirring rate of 120r/min~180r/min to obtain copper ferrite sol State mixed liquid.

The other steps are the same as the first or second embodiment.

Specific embodiment four: this embodiment is different from one of specific embodiments one to three in that: in step two, under the temperature condition of 90℃～100℃, the rate of 10mg/s～20mg/s is added to copper ferrite Add natural zeolite powder to the sol mixed liquid, continue to stir at a stirring rate of 120r/min-180r/min until the copper ferrite sol mixed liquid evaporates to dryness.

The other steps are the same as those in the first to third specific embodiments.

Specific embodiment five: This embodiment is different from one of specific embodiments 1 to 4 in that: the natural zeolite powder described in step 2 is prepared in the following steps: natural zeolite with the same particle size is taken, crushed by a high-speed pulverizer, and then sequentially Wash with pure water and 0.1 mol/L hydrochloric acid to obtain natural zeolite powder.

The other steps are the same as those in the first to fourth specific embodiments.

Embodiment 6: The difference between this embodiment and one of Embodiments 1 to 5 is: in step 2, the temperature is increased to 400° C. at a heating rate of 3° C./min, and it is calcined at 400° C. for 8 hours.

The other steps are the same as those in the first to fifth specific embodiments.

Embodiment 7: The difference between this embodiment and Embodiments 1 to 6 is that the copper ferrite spinel supported on the copper ferrite/zeolite spinel composite material described in step 2 has a particle size of 2 μm ～30μm.

The other steps are the same as those in the first to sixth specific embodiments.

Embodiment 8: This embodiment is different from one of Embodiments 1 to 7 in that the mass ratio of copper ferrite to natural zeolite powder in the copper ferrite sol mixed liquid in step 2 is 1:1.

The other steps are the same as in the first to seventh specific embodiments.

Specific embodiment 9: Application of copper ferrite/zeolite spinel composite material. The copper ferrite/zeolite spinel composite material is used as a catalyst to catalyze ozone oxidation and degradation of atrazine in water.

Embodiment 10: This embodiment is different from Embodiment 9 in that: when the copper ferrite/zeolite spinel composite material is used as a catalyst, the addition amount is 0.05 g/L to 1.0 g/L.

The other steps are the same as in the ninth embodiment.

The following examples are used to verify the beneficial effects of the present invention:

Example 1: The preparation method of copper ferrite/zeolite spinel composite material is completed according to the following steps:

1. Put 120mL of absolute ethanol in a water bath, add 3.83mmol copper nitrate and 7.66mmol ferric nitrate to 120mL of absolute ethanol at a temperature of 95°C, stir evenly at a stirring rate of 180r/min, and then Add 7.66mmol of anhydrous citric acid, and then stir evenly at a stirring rate of 180r/min to obtain a copper ferrite sol-state mixture;

2. Under the temperature condition of 95℃, add natural zeolite powder to the copper ferrite sol mixture at a rate of 10mg/s, and continue to stir at a stirring rate of 180r/min until the copper ferrite sol mixture is evaporated to dryness. Then it was ground, placed in a muffle furnace, heated to 400°C at a heating rate of 3°C/min, and calcined at 400°C for 8 hours, finally cooled to room temperature in air, and ground to obtain copper ferrite/zeolite tip The copper ferrite spinel supported on the copper ferrite/zeolite spinel composite material has a particle size of 2 μm to 30 μm, and the copper ferrite sol-state mixture contains the copper ferrite and natural zeolite The mass ratio of powder is 1:1.

The natural zeolite powder described in step two is prepared according to the following steps: natural zeolite with uniform particle size is taken, crushed by a high-speed pulverizer, and then washed with pure water and 0.1 mol/L hydrochloric acid in sequence to obtain natural zeolite powder.

Embodiment 2: The preparation method of copper ferrite/zeolite spinel composite material is completed according to the following steps:

2. Under the temperature condition of 95℃, add natural zeolite powder to the copper ferrite sol mixture at a rate of 10mg/s, and continue to stir at a stirring rate of 180r/min until the copper ferrite sol mixture is evaporated to dryness. Then it was ground, placed in a muffle furnace, heated to 400°C at a heating rate of 3°C/min, and calcined at 400°C for 8 hours, finally cooled to room temperature in air, and ground to obtain copper ferrite/zeolite tip The copper ferrite spinel supported on the copper ferrite/zeolite spinel composite material has a particle size of 2 μm-30 μm, and the copper ferrite sol-state mixture contains the copper ferrite and natural zeolite The mass ratio of powder is 1:2.

Example 3: The preparation method of copper ferrite/zeolite spinel composite material is completed according to the following steps:

2. Under the temperature condition of 95℃, add natural zeolite powder to the copper ferrite sol mixture at a rate of 10mg/s, and continue to stir at a stirring rate of 180r/min until the copper ferrite sol mixture is evaporated to dryness. Then it was ground, placed in a muffle furnace, heated to 400°C at a heating rate of 3°C/min, and calcined at 400°C for 8 hours, finally cooled to room temperature in air, and ground to obtain copper ferrite/zeolite tip The copper ferrite spinel supported on the copper ferrite/zeolite spinel composite material has a particle size of 2 μm to 30 μm, and the copper ferrite sol-state mixture contains the copper ferrite and natural zeolite The mass ratio of powder is 1:5.

Comparative Test:

Under the condition of 20℃, select six 500mL reactors (1#～6#):

In the 1# reactor, first add ultrapure water and 10mmol/L borax buffer solution with a pH of 7, and then add the copper ferrite/zeolite spinel composite prepared in Example 1 at a ratio of 0.20g/L , And finally add 2μmol/L atrazine, the moment the ozone is introduced, the reaction starts timing, and take points at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.

In the 2# reactor, first add ultrapure water and 10mmol/L borax buffer solution with a pH of 7, and then add the copper ferrite/zeolite spinel composite prepared in Example 2 at a ratio of 0.20g/L , And finally add 2μmol/L atrazine, the moment the ozone is introduced, the reaction starts timing, and take points at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.

In the 3# reactor, first add ultrapure water and 10mmol/L borax buffer solution with a pH of 7, and then add the copper ferrite/zeolite spinel composite prepared in Example 3 at a ratio of 0.20g/L , And finally add 2μmol/L atrazine, the moment the ozone is introduced, the reaction starts timing, and take points at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.

In the 4# reactor, first add ultrapure water and 10mmol/L borax buffer solution with a pH of 7, then add the natural zeolite catalyst at a ratio of 0.20g/L, and finally add 2μmol/L atrazine, At the moment of ozone entering, the reaction starts timing, and points are taken at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.

In the 5# reactor, first add ultrapure water and 10mmol/L borax buffer solution with a pH of 7, then add copper ferrite catalyst at a ratio of 0.20g/L, and finally add 2μmol/L atrazine. The moment the ozone is introduced, the reaction starts timing, and points are taken at 0min, 2min, 5min, 10min, 20min, 30min and 40min respectively.

In the 6# reactor, first add ultrapure water and 10mmol/L borax buffer solution with a pH of 7, and then add 2μmol/L atrazine. The moment the ozone is introduced, the reaction starts timing, at 0min, 2min , 5min, 10min, 20min, 30min and 40min take points respectively.

Figure 1 is a comparison diagram of the removal efficiency of atrazine in the 1#～6# reactor in the comparative test; as shown in Figure 1, it is the same as a single ozone system, a single natural zeolite catalyzed ozone system and a single copper ferrite catalyzed ozone Compared with the system, the copper ferrite/zeolite spinel composite materials prepared in Example 1 to Example 3 show very high catalytic activity. Within 40 minutes of reaction time, the removal rate of atrazine in water is relatively high. The effect of ozone is increased by about 30%, and it has high chemical stability. Only trace amounts of copper and iron ions are detected in the aqueous solution after the reaction, which can be used in the actual water treatment field. However, the copper ferrite/zeolite catalyst has no obvious adsorption effect; and the ozone oxidation alone can only degrade a small amount of atrazine; therefore, the copper ferrite/zeolite spinel composite material prepared in Examples 1 to 3 is made Simple, low cost, simple operation and high catalytic efficiency.

Figure 2 is a graph showing the removal efficiency of atrazine from water in the copper ferrite/zeolite spinel composite material prepared in Example 1 within 0 to 120 minutes; as shown in Figure 2, the copper ferrite/zeolite spinel composite material prepared in Example 1 The zeolite spinel composite material completely degrades the atrazine in the water at 120 minutes.

Claims

The preparation method of copper ferrite/zeolite spinel composite material is characterized in that the preparation method is completed in the following steps:

1. Under the temperature condition of 90℃～100℃, add copper nitrate and ferric nitrate to absolute ethanol, stir evenly, then add anhydrous citric acid, and stir evenly to obtain copper ferrite sol state mixture, so The molar ratio of copper nitrate to ferric nitrate is 1:2, the ratio of the total amount of copper nitrate and ferric nitrate to the volume of anhydrous ethanol is 11.49mmol: (100mL～120mL), the volume of anhydrous ethanol is relative to that of anhydrous ethanol. The ratio of the amount of citric acid is (100mL～120mL): 7.66mmol;

2. Under the temperature condition of 90℃～100℃, add natural zeolite powder to the copper ferrite sol mixture at a rate of 10mg/s～20mg/s, and continue to stir until the copper ferrite sol mixture is evaporated to dryness. Then it was ground, heated to 400°C, and calcined at 400°C for 8 hours, and finally cooled to room temperature in air, and ground to obtain a copper ferrite/zeolite spinel composite material. The copper ferrite sol-state mixture contained iron The mass ratio of acid copper to natural zeolite powder is 1:(1～5).
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, characterized in that in step 1, the copper nitrate and iron nitrate are added to the anhydrous under the temperature condition of 90°C to 100°C. In ethanol, stir evenly at a stirring rate of 120r/min to 180r/min.
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, characterized in that in step one, anhydrous citric acid is added, and then stirred evenly at a stirring rate of 120r/min to 180r/min, The copper ferrite sol state mixed liquid is obtained.
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, characterized in that in step 2, under the temperature condition of 90°C to 100°C, at a rate of 10 mg/s to 20 mg/s Add natural zeolite powder to the copper ferrite sol state mixture, and continue to stir at a stirring rate of 120r/min to 180r/min until the copper ferrite sol state mixture is evaporated to dryness.
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, characterized in that the natural zeolite powder described in step 2 is prepared by the following steps: natural zeolite with the same particle size is taken and passed through a high-speed pulverizer It is crushed, and then washed with pure water and 0.1 mol/L hydrochloric acid in sequence to obtain natural zeolite powder.
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, characterized in that in step 2, the temperature is increased to 400°C at a heating rate of 3°C/min, and the temperature is 400°C. Calcined for 8h.
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, characterized in that the copper ferrite spinel supported on the copper ferrite/zeolite spinel composite material in step two is The particle size is 2 μm to 30 μm.
The method for preparing copper ferrite/zeolite spinel composite material according to claim 1, wherein the mass ratio of copper ferrite to natural zeolite powder in the copper ferrite sol-state mixture in step two is 1:1 .
The application of the copper ferrite/zeolite spinel composite material is characterized in that the copper ferrite/zeolite spinel composite material is used as a catalyst to catalyze ozone oxidation and degradation of atrazine in water.
The application of the copper ferrite/zeolite spinel composite material according to claim 9, wherein when the copper ferrite/zeolite spinel composite material is used as a catalyst, the addition amount is 0.05g/L～1.0g/ L.